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Nguyen, Duc Anh - One of the best experts on this subject based on the ideXlab platform.
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Macromonomères cycloalcéniques synthétisés à partir d'inimers multifonctionnels originaux : une plateforme pour l'élaboration de copolymères gréffés, en goupillon ou de type "mikto-arm"
2016Co-Authors: Nguyen, Duc AnhAbstract:Le sujet de cette thèse concerne l'élaboration de macromonomères, de copolymères greffés et de polymères étoiles de type 'mikto-arm'. De telles architectures macromoléculaires ont été synthétisées par la combinaison de techniques de polymérisation contrôlées/vivantes telles que la polymérisation par ouverture de cycle (par métathèse) (RO(M)P) etde chimie 'click' orthogonales : cycloaddition 1,3-dipolaireazoturealcyne catalysée au cuivre (CuAAC) et thiol-ène.Dans un premier temps, des macromonomères originaux à fonctionnalité polymérisable (oxa)norbornène portant deux chaînes macromoléculaires poly(e-caprolactone) (PCL) et/ou poly(oxyde d'éthylène) (POE) ont été synthétisés par combinaison ROP/CuAAC. Les macromonomères à fonctionnalité (oxa)norbornène avec deux chaînes PCL de masse molaire moyenne en nombre (Mn) compris entre 1400 et 5000 g/mol ont été obtenus par ROP organocatalysée. La synthèse des macromonomères POE44-b-PCLn à fonctionnalité norbornène avec un bloc PCL de longueur variable (1100 g/mol
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Macromonomères cycloalcéniques synthétisés à partir d'inimers multifonctionnels originaux : une plateforme pour l'élaboration de copolymères gréffés, en goupillon ou de type "mikto-arm"
HAL CCSD, 2016Co-Authors: Nguyen, Duc AnhAbstract:The objective of the present thesis was the preparation of complex macromolecules by the combination of controlled/livingpolymerization methods such as ring-opening (metathesis) polymerization (RO(M)P) and highly efficient orthogonal chemistries: copper-catalyzed azide-alkyne coupling (CuAAC) and thiol-ene reactions.In the first part of this work, a series of well-defined structural (co)polymers containing a cycloolefin (norbornene (NB) oroxanorbornene (ONB)) functionality bearing two polymer chains including poly(ε-caprolactone) (PCL) and/or poly(ethylene oxide) (PEO) have been successfully prepared using the combination of ring-opening polymerization (ROP) and CuAAC ‘click’ chemistry. Well-defined (oxa)norbornenyl-functionalized bis-PCL polymers with PCL chain ranging from 1400 to 5000 g/mol were obtained by organocatalyst-mediated ROP. Norbornenyl-functionalized PEO-b-PCL block copolymers with PCL block in the range 1100 to 4100 g/mol were synthesized from commercially available PEO 2000 g/mol by CuAAC followed by ROP of CL. The presence of a hydrophilic PEO chain and a hydrophobic PCL chain in norbornenylfunctionalizedPEO-b-PCL copolymers gives rise to self-assembling properties in water solution. Critical micellar concentrations (CMC)are in the range of 0.08 – 0.006 g/L for copolymers with PCL chain length ranging from 10 to 36 CL units, respectively. Thecorresponding micelles show hydrodynamic diameters in range of 10 – 23 nm with low polydispersities.In the second part of this work, well-defined copolymers were used to prepare bottle-brush and (mikto-arm) star copolymersthrough reactions involving the cycloolefin functionality. On the one hand, high density grafting bottle-brush copolymerspoly(oxa)norbornene-g-bisPCL, polynorbornene-g-PEO/PCL (PNB-g-(PEO/PCL)) and PNB-b-(PNB-g-(PEO/PCL)) were achieved by ROMP according to the ‘grafting through’ strategy using Grubbs’ catalysts. On the other hand, PCL, PEO, PNIPAM-based 3-arms star, 4-arms star copolymers were obtained via radical thiol-ene reactions as demonstrated by 1H NMR, SEC and MALDI-ToF MS analysis.The high reactivity of these copolymers toward ROMP and thiol-ene reactions makes them interesting candidates in order toprepare new well-defined copolymers with controlled structures and properties through highly efficient synthetic strategies.Le sujet de cette thèse concerne l'élaboration de macromonomères, de copolymères greffés et de polymères étoiles de type 'mikto-arm'. De telles architectures macromoléculaires ont été synthétisées par la combinaison de techniques de polymérisation contrôlées/vivantes telles que la polymérisation par ouverture de cycle (par métathèse) (RO(M)P) etde chimie 'click' orthogonales : cycloaddition 1,3-dipolaireazoturealcyne catalysée au cuivre (CuAAC) et thiol-ène.Dans un premier temps, des macromonomères originaux à fonctionnalité polymérisable (oxa)norbornène portant deux chaînes macromoléculaires poly(e-caprolactone) (PCL) et/ou poly(oxyde d'éthylène) (POE) ont été synthétisés par combinaison ROP/CuAAC. Les macromonomères à fonctionnalité (oxa)norbornène avec deux chaînes PCL de masse molaire moyenne en nombre (Mn) compris entre 1400 et 5000 g/mol ont été obtenus par ROP organocatalysée. La synthèse des macromonomères POE44-b-PCLn à fonctionnalité norbornène avec un bloc PCL de longueur variable (1100 g/mol
Mitsufumi Nodono - One of the best experts on this subject based on the ideXlab platform.
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radical copolymerization of methyl 2 norbornene 2 carboxylate and 2 phenyl 2 norbornene with styrene alkyl acrylate and methyl methacrylate facile incorporation of Norbornane framework into polymer main chain and its effect on glass transition temperature
Polymer, 2010Co-Authors: Eiji Ihara, Shingo Honjyo, Koh Kobayashi, Satoru Ishii, Tomomichi Itoh, Kenzo Inoue, Hikaru Momose, Mitsufumi NodonoAbstract:Abstract Radical copolymerization behavior of methyl 2-norbornene-2-carboxylate 1 and 2-phenyl-2-norbornene 2 was investigated. Radical copolymerization of 1 and 2 with styrene, alkyl acrylate, and methyl methacrylate in a variety of monomer combinations afforded copolymers, whose main chains consisted of Norbornane framework. Relative monomer reactivity ratios for the copolymerization of 1 and 2 with n -butyl acrylate ( n -BA) were determined by the Fineman–Ross method. Temperature-modulated DSC analysis for poly( 1 or 2 - co - n -BA)s revealed remarkable T g -raising effect of incorporation of Norbornane framework into the polymer main chain, compared to that effect of styrene repeating unit.
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radical copolymerization of alkyl 2 norbornene 2 carboxylate with alkyl acrylates facile incorporation of Norbornane framework into poly alkyl acrylate s
Journal of Polymer Science Part A, 2007Co-Authors: Eiji Ihara, Shingo Honjyo, Tomomichi Itoh, Kenzo Inoue, Mitsufumi NodonoAbstract:Radical copolymerization of alkyl 2-norbornene-2-carboxylates (alkyl = Me 1a, nBu 1b) with alkyl acrylates (alkyl = ethyl, methyl, and n-butyl) was investigated. Copolymerization of 1a,b with the alkyl acrylates initiated by 1,1'-azobis (cyclohexane-1-carbonitrile) at 85 °C proceeded to give random copolymers, although the homopolymerization of 1a,b did not proceed efficiently under the same conditions. Typically, bulk copolymerization of 1a with ethyl acrylate in a feed ratio of 1:3 ([1a]:[EA]) afforded a copolymer with M n = 33,300 containing 19.4 mol % of la unit in the composition. An increase of T g derived from the incorporation of the rigid Norbornane framework was observed, although the extent of the temperature rise was rather moderate. The ternary radical copolymerization of 1a,b/alkyl acrylate/N-phenyl-maleimide proceeded to give copolymers with the three repeating units in the main chain.
Yukio Imanishi - One of the best experts on this subject based on the ideXlab platform.
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synthesis of poly macromonomer s by repeating ring opening metathesis polymerization romp with mo chcme2ph nar or 2 initiators
Macromolecules, 2001Co-Authors: Kotohiro Nomura, Shinya Takahashi, Yukio ImanishiAbstract:Various poly(macromonomer)s of ring-opened poly(norbornene) backbone containing ring-opened poly(norbornene) derivatives in the side chain have been prepared efficiently by repeating the ring-opening metathesis polymerizations (ROMP) using well-defined molybdenum initiator of the type, Mo(CHCMe2Ph)(N-2,6-iPr2C6H3)(OR)2 [OR = OCMe3, OCMe(CF3)2]. The key steps for synthesis of the macromonomer are both exclusive end-capping and quantitative esterification of hydroxy group at the polymer chain end with norbornene carboxylic acid chloride, and the use of Mo(CHCMe2Ph)(N-2,6-iPr2C6H3)[OCMe(CF3)2]2 was found to be an effective initiator in order for this polymerization to proceed to the complete conversion. The present synthetic approach should be useful for preparing various poly(macromonomer)s containing functional groups, especially amphiphilic poly(macromonomer) architectures precisely.
Eiji Ihara - One of the best experts on this subject based on the ideXlab platform.
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radical copolymerization of methyl 2 norbornene 2 carboxylate and 2 phenyl 2 norbornene with styrene alkyl acrylate and methyl methacrylate facile incorporation of Norbornane framework into polymer main chain and its effect on glass transition temperature
Polymer, 2010Co-Authors: Eiji Ihara, Shingo Honjyo, Koh Kobayashi, Satoru Ishii, Tomomichi Itoh, Kenzo Inoue, Hikaru Momose, Mitsufumi NodonoAbstract:Abstract Radical copolymerization behavior of methyl 2-norbornene-2-carboxylate 1 and 2-phenyl-2-norbornene 2 was investigated. Radical copolymerization of 1 and 2 with styrene, alkyl acrylate, and methyl methacrylate in a variety of monomer combinations afforded copolymers, whose main chains consisted of Norbornane framework. Relative monomer reactivity ratios for the copolymerization of 1 and 2 with n -butyl acrylate ( n -BA) were determined by the Fineman–Ross method. Temperature-modulated DSC analysis for poly( 1 or 2 - co - n -BA)s revealed remarkable T g -raising effect of incorporation of Norbornane framework into the polymer main chain, compared to that effect of styrene repeating unit.
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radical copolymerization of alkyl 2 norbornene 2 carboxylate with alkyl acrylates facile incorporation of Norbornane framework into poly alkyl acrylate s
Journal of Polymer Science Part A, 2007Co-Authors: Eiji Ihara, Shingo Honjyo, Tomomichi Itoh, Kenzo Inoue, Mitsufumi NodonoAbstract:Radical copolymerization of alkyl 2-norbornene-2-carboxylates (alkyl = Me 1a, nBu 1b) with alkyl acrylates (alkyl = ethyl, methyl, and n-butyl) was investigated. Copolymerization of 1a,b with the alkyl acrylates initiated by 1,1'-azobis (cyclohexane-1-carbonitrile) at 85 °C proceeded to give random copolymers, although the homopolymerization of 1a,b did not proceed efficiently under the same conditions. Typically, bulk copolymerization of 1a with ethyl acrylate in a feed ratio of 1:3 ([1a]:[EA]) afforded a copolymer with M n = 33,300 containing 19.4 mol % of la unit in the composition. An increase of T g derived from the incorporation of the rigid Norbornane framework was observed, although the extent of the temperature rise was rather moderate. The ternary radical copolymerization of 1a,b/alkyl acrylate/N-phenyl-maleimide proceeded to give copolymers with the three repeating units in the main chain.
Mikhail A. Tlenkopatchev - One of the best experts on this subject based on the ideXlab platform.
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polynorbornene with pentafluorophenyl imide side chain groups synthesis and sulfonation
Journal of Polymer Science Part A, 2010Co-Authors: Arlette A. Santiago, Joel Vargas, Rubén Gaviño, Serguei Fomine, Mikhail A. TlenkopatchevAbstract:The mixtures of exo-endo-monomers and isomerically pure endo-monomers of N-pentafluorophenyl-norbornene-5,6-dicarboximide (2a) and N-phenyl-norbornene-5,6-dicarboximide (2b) were synthesized and polymerized via ring opening metathesis polymerization using bis(tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride (I) and tricyclohexylphosphine [1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][benzylidene] ruthenium dichloride (II). Ring opening metathesis polymerization of mixtures of exo-endo-monomers (2a) and (2b) and pure endo-2b gave the corresponding high molecular weights poly(N-pentafluorophenyl-norbornene-5,6-dicarboximide) (3a) and poly(N-phenyl-norbornene-5,6-dicarboximide) (3b). The isomerically pure endo-2a did not polymerize by I in these conditions, since I is the least active catalyst and endo-2a is the least active monomer because of the intramolecular complex formation between the Ru active center and the fluorine atom of ring-opened endo-2a on the one hand and steric hindrances caused by the pentafluorinated ring on the other. The quantitative hydrogenation of the polymer 3a, at room temperature and 115 bar, was achieved by a Wilkinson's catalyst. The new polynorbornene bearing highly fluorinated sulfonic acid groups (5) was obtained by the reaction of the hydrogenated poly(N-pentafluorophenyl-norbornene-5,6-dicarboximide) (4) with sodium 4-hydroxybenzenesulfonate dihydrate. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2925–2933, 2010
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synthesis of high tg polymers by ring opening metathesis polymerization of n cycloalkylnorbornene dicarboximide
Macromolecular Chemistry and Physics, 2002Co-Authors: Armando Pineda Contreras, Alfredo Masiel Cerda, Mikhail A. TlenkopatchevAbstract:Ring-opening metathesis polymerization (ROMP) of N-(1-adamantyl)-exo-norbornene-5,6-dicarboximide (AdNDI) (3a) and N-cyclohexyl-exo-norbornene-5,6-dicarboximide (ChNDI) (3b) was performed using well-defined vinylidene ruthenium (II) catalysts Cl2(PR3)2RuCCH(t-Bu) (R = Ph and Cy). The homopolymer of 3a showed a Tg of 271 °C while poly-ChNDI of 3b had a Tg of 129 °C. Copolymers of these monomers with norbornene (NB) demonstrated significant Tg increases compared to unsubstituted poly-NB. Analysis of copolymers of 3a and NB isolated at the initial stages of copolymerization showed that both monomers were incorporated randomly and displayed very similar reactivity. ROMP of 3a and 3b.
